Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L43/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing boron, silicon, phosphorus, selenium, tellurium or a metal; Compositions of derivatives of such polymers
  • C08L43/04—Homopolymers or copolymers of monomers containing silicon
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4085—Curing agents not provided for by the groups C08G59/42 - C08G59/66 silicon containing compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences

Definitions

• the present invention relates to a curable resinous composition comprising an epoxy resin and an organic elastomeric polymer having at least one silicon-containing reactive group in a molecule. More particularly, it relates to a curable resinous composition comprising an epoxy resin, an organic elastomeric polymer having at least one silicon-containing reactive group in a molecule, a silicone compound having a silicon-containing reactive group and a functional group reactive with an epoxy group, and a curing agent for the epoxy resin, which affords a cured product having improved mechanical properties such as flexibility, impact resistance, toughness and strength.
• An epoxy resin finds various applications such as a molding material, an adhesive, a coating, a plywood, a laminate and the like. However, in these applications, it generally has a drawback such that it affords a cured product having brittleness and poor peeling strength.
• An organic elastomeric polymer having at least one silicon-containing reactive group in a molecule has such an interesting characteristic that it can be cured even at a room temperature to give an elastomer.
• the cured elastomer has poor strength, which prevents its wide application.
• An object of the present invention is to provide a curable resinous composition comprising an epoxy resin and an organic elastomeric polymer having a silicon-containing reactive group by which the brittleness and peeling strength of the epoxy resin and strength of the organic polymer are improved.
• the present invention provides a curable resinous composition
• a curable resinous composition comprising:
• the present invention is based on the finding that the addition of the silicone compound (C) to a composition of the organic elastomeric polymer (A) and the epoxy resin (B) is very important to improve brittleness of the epoxy resin and strength of the polymer (A).
• organic elastomeric polymer having at least one silicon-containing reactive group in a molecule are polyethers prepared by ring opening polymerization of cyclic ethers (e.g. propyleneoxide, ethyleneoxide, tetrahydrofuran and the like); polyesters prepared by polycondensation of a dibasic acid (e.g.
• adipic acid and glycol or ring opening polymerization of lactons; ethylene/propylene copolymers; polyisobutylene and copolymers of isobutylene with isoprene and the like; polychloroprene; polyisoprene and copolymers of isoprene with butadiene, styrene, acrylonitrile and the like; polybutadiene and copolymers of butadiene with styrene, acrylonitrile and the like; polyolefins prepared by hydrogenating polyisoprene, polybutadiene or isoprene/butadiene copolymers; polyacrylates prepared by radical polymerization of acrylate (e.g.
• ethyl acrylate, butyl acrylate and the like and copolymers of acrylate with vinyl acetate, acrylonitrile, styrene, ethylene and the like; graft polymers prepared by polymerizing a vinyl monomer in the organic elastomeric polymer (A); polysulfides; and the like.
• polyethers comprising repeating units of the formula: -R-0- wherein R is a C 1 -C 4 alkylene group (e.g. polypropyleneoxide and the like); graft polymers prepared by polymerizing a vinyl monomer (e.g.
• polyether e.g. polypropyleneoxide and the like
• polyalkyl acrylate or copolymers of at least 50 % by weight of alkyl acrylate with vinyl acetate, acrylonitrile, styrene, ethylene and the like since they can introduce the silicon-containing reactive group at a chain end of the molecule and are suitable for the preparation of a liquid polymer in the absence of a solvent.
• polypropyleneoxide is preferable since it imparts water resistance to the cured product and is cheap and easily handled as a liquid material.
• the silicon-containing reactive group is represented by the formula: wherein X is a hydroxyl group or a hydrolyzable group, R is a monovalent hydrocarbon group having 1 to 20 carbon atoms or an organosiloxy group, "a” is 0, 1, 2 or 3, "b” is 0, 1 or 2 provided that the total of "a” and “b” is at least 1, preferably from 1 to 4, and "m” is 0 or an integer of 1 to 18.
• the group (I) When X is the hydrolyzable group, the group (I) is cross linked through hydrolysis by water and a silanol condensation reaction in the presence or absence of a catalyst for the silanol condensation. When X is a hydroxyl group, the group (I) is cross linked through the silanol condensation reaction in the presence or absence of a catalyst for silanol condensation.
• the hydrolyzable group are a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an aminoxy group, a mercapto group, an alkenyloxy group and the like.
• the alkoxy group is preferable since it is mildly hydrolyzed and easily handled.
• the silicon-containing reactive group has at least one silicon atom.
• the silicon-containing reactive group preferably not more than 20 silicon atoms.
• R when R is the organosiloxy group, it may be an triorgancsiloxy group of the formula: wherein R' is, the same or different, a C 1 -C 20 monovalent hydrocarbon group.
• silicon-containing reactive group (I) a group of the formula: wherein R and X are the same as defined above, and "a" is 1, 2 or 3 is preferable.
• the silicon-containing reactive group (I) chemically bonds to the backbone chain of the organic elastomeric polymer. It is not preferable for the silicon-containing reactive group to be bonded to the backbone chain through an bond structure of the formula: ⁇ Si-O-C ⁇ , since such structure tends to be cleavaged by water.
• a preferable bonding structure between the silicon atom of the reactive group and the backbone chain is, for example, a structure of the formula: ⁇ Si-C ⁇ .
• the reactive group is bonded to the backbone chain in the following chemical structure: wherein R 1 , X, a, b and m are the same as defined above.
• R 2 is a hydrogen atom or a C 1 -C 20 monovalent organic group
• R 3 is a C 1 -C 20 divalent organic group
• "c" is 0 or 1.
• the silicon-containing reactive group may be introduced in the organic elastomeric polymer by following manners;
• polystyrene resin polystyrene resin
• polyetherpolyols comprising repeating units of the formula: -R-0- wherein R is a C2-C4 alkylene group (e.g. polypropylenepolyol, pclyethylenepolycl, poly- tetramethylenediol and the like); polyesterpolyols prepared by polycondensation of a dibasic acid (e.g.
• adipic acid and glycol or ring opening polymerization of lactons
• polyols or polycarboxylic acids of polyisobutylene polyols or polycarboxylic acids of polybutadiene or copolymers of butadiene with styrene, acrylonitrile and the like
• polyols of polyolefins prepared by hydrogenating polyisoprene or polybutadiene
• polymer having an isocyanate functional group prepared by reacting the above polyols or polycarboxylic acids with polyisocyanate
• polymers having an ethylenically unsaturated bond prepared by reacting the above polyols with a halogen-containing ethylenically unsaturated compound, and the like.
• preferable are those having the functional group Y at the chain end of the molecule.
• the silicon-containing compound having the functional group Y' are amino group-containing silanes (e.g. Y-(2-aminoethyl)aminopropyltrimethoxysilane, ⁇ -(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -aminopropyltriethoxysilane and the like); mercapto group-containing silanes (e.g. Y-mercaptopropyltrimethoxysilane, Y-mercaptopropylmethyldimethoxysilane and the like); epoxysilanes (e.g.
• a combination of the polymer having an isocyanate group and the amino group- or mercapto group-containing silane and (ii) a combination of the polymer having an ethylenically unsaturated group and the hydrosilane are preferable.
• a combination of polypropyleneoxide having an allylether group at the chain end and the hydrosilane is particularly preferable.
• a silyl group can be introduced in the polymer by a hydrosilylation reaction in the presence of a platinum catalyst.
• the organic polymer (A) has at least one, preferably 1.2 to 6 silicon-containing reactive groups in a molecule on the average.
• the silicon-containing reactive group is attached to the chain end of the organic polymer molecule, because the terminal silicon-containing reactive group elongates the chain length between the adjacent cross linking sites in the cured product so that, on one hand, the brittleness of the epoxy resin is more effectively improved, and on the other hand, the elastomeric cured product comprising predominantly the polymer (A) has better strength.
• the molecular weight of the organic polymer (A) is usually from 500 to 50,000, preferably from 1,000 to 20,000 since in this molecular weight range, the polymer is in a liquid state.
• the silicon-containing reactive group having a silicon atom to which a hydroxyl group is attached may be prepared by hydrolyzing the silicon-containing reactive group having a silicon atom to which a hydrolyzable group is attached.
• organic polymer (A) are disclosed in U.S. Patent Nos. 3,408,321, 3,453,230 and 3,592,795, Japanese Patent Publication No. 32673/1974, Japanese Patent Kokai Publication (unexamined) Nos. 156599/1975, 73561/1976, 6096/1979, 13767/1980, 13768/1980, 82123/1980, 123620/1980, 125121/1980, 131021/1980, 131022/1980, 135135/1980, 137129/1980, 179210/1982, 1 91703/1983, 7 8 220/1984, 78221/1984, 78222/1984, 78223/1984 and 1680 1 4/1984.
• the epoxy resin (B) may be any one of conventionally used ones.
• Specific examples of the epoxy resin (B) are flame-retardant epoxy resins (e.g. epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, glycidyl ether of tetrabromobisphenol A and the like), novolak type epoxy resins, hydrogenated bisphenol A type epoxy resins, epoxy resins of the type of glycidyl ether of bisphenol A-propyleneoxide adduct, glycidyl p-oxybenzoate type epoxy resin, m-aminophnol type epoxy resins, diaminodiphenylmethane type epoxy resins, urethane modified epoxy resins, alicyclic epoxy resins, glycidyl ether of polyhydric alcohol (e.g.
• those having two epoxy groups of the formula: in a molecule are preferable since they are highly reactive during curing and the cured product easily forms a three dimensional network.
• Most preferable are the bisphenol A type epoxy resins and the novolak type epoxy resins.
• the curing agent (D) for the epoxy resin used according to the present invention may be any one of the conventionally used ones.
• Specific examples of the curing agent are amines (e.g. triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperazine, m-xylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, 2,4,6-tris-(dimethylaminomethyl)phenol and the like); tert-amine salts; polyamide resins; imidazoles; dicyanediamides; complex compounds of boron trifluoride, carboxylic acid anhydrides (e.g.
• phthalic anhydride hexahydrophthalic anhydride, tetrahydrophthalic anhydride, endomethylenetetrahydro- phthalic anhydride, dodecinyl succinic anhydride, pyromellitic anhydride, chlorendic anhydride and the like); alcohols; phenols; and carboxylic acids.
• the amount of the curing agent (D) varies with the kinds of the epoxy resin and/or the curing agent. Usually, 0.1 to 300 parts by weight of the curing agent (D) is used based on 100 parts by weight of the epoxy resin (B).
• the resinous composition according to the present invention contains the silicone compound having a silicon-containing reactive group and a functional group reactive with an epoxy group (C) as one of the essential components.
• Examples of the functional group reactive with the epoxy group are a primary, secondary or tertiary amino group, a mercapto group, an epoxy group and a carboxyl group.
• the silicon-containing reactive group is the same as that of the organic polymer (A). Particularly, the alkoxysilyl group is preferable due to its good handling properties.
• silicone compound (C) are amino group-containing silanes (e.g. Y-aminopropyltrimethoxysilane, Y-aminopropyltriethoxysilane, Y-aminopropylmethyldimethoxysilane, Y-(2-aminoethyl)aminopropyltrimethoxysilane, Y-(2-aminoethyl)aminopropylmethyldimethoxysilane, ⁇ -(2-aminoethyl)aminopropyltriethoxysilane, ⁇ -ureidopropyltriethoxysilane, N- ⁇ -(N-vinylbenzylaminoethyl)-Y-aminopropyltrimethoxysilane, ⁇ -anilinopropyltrimethoxy- silane and the like); mercapto group-containing silanes (e.g.
• silane compound may be used alone or as a mixture with at least one other silane compound.
• a weight ratio of the epoxy resin (B) to the organic polymer (A) is from 100:1 to 1:100.
• the amount of the organic polymer (A) is less than the lower limit, impact strength or toughness of the cured product is not desirably improved.
• the amount of the organic polymer (A) exceeds the upper limit, the strength of the cured product is insufficient.
• a preferable weight ratio of the epoxy resin (B) to the organic polymer (A) varies with the final use of the cured product.
• 1 to 100 parts by weight preferably 5 to 100 parts by weight of the organic polymer (A) is used based on 100 parts by weight of the epoxy resin (B).
• 1 to improve strength of the cured organic elastomeric polymer 1 to 200 parts by weight, preferably 5 tc 1'00 parts by weight of the epoxy resin is used based on 100 parts by weight of the organic polymer (A).
• the amount of the silicone compound (C) is sc selected that a weight ratio of the total weight of the organic polymer (A) and the epoxy resin (B) to the weight of the silicone compound (C), i.e. (A + B)/C, is from 100:0.1 to 100:20, preferably from 100:0.2 to 100:10.
• the curable resinous composition of the invention may be prepared by mixing the four components (A), (B), (C) and (D) according to a conventional method.
• the components are mixed with a mixer, rolls or a kneacer at a room or elevated temperature.
• the components are dissolved in a suitable solvent and mixed.
• a suitable combination of the components By a suitable combination of the components, a one pack type or two pack type composition can be prepared.
• the composition of the invention may optionally contains other conventionally used additives such as a filler, a plasticizer, a silanol condensation catalyst for curing the organic polymer (A), an anti-aging agent, a ultraviolet absorbing agent, a lubricant, a pigment, a foaming agent .and the like.
• a filler such as a plasticizer, a silanol condensation catalyst for curing the organic polymer (A), an anti-aging agent, a ultraviolet absorbing agent, a lubricant, a pigment, a foaming agent .and the like.
• the filler are wood meal, pulp, cotton chip, asbestos, glass fiber, carbon fiber, mica, walnut shell flour, rice hull flour, graphite, diatomaceous earth, china clay, fumed silica, precipitated silica, silicic anhydride, carbon black, calcium carbonate, clay, talc, titanium oxide, magnesium carbonate, quartz powder, aluminum powder, flint powder, zinc powder, and mixtures thereof.
• the curable composition of the invention can be cured at a room temperature although the curing rate is increase at an elevated temperature of 100 to 150°C.
• the epoxy resin (B) and the curing agent (C) are so selected.
• the liquid epoxy resin is used, a non-solvent type curable composition of the invention is prepared.
• composition of the present invention may be formed by a conventional molding method.
• the composition contains the epoxy resin (B) in an amount larger than that of the organic polymer (A), it is preferably molded by the same method as used for molding the epoxy resin, for example, compression molding, transfer molding and injection molding. Thereby, a molded article and a laminated article (e.g. copper-clad laminate and compressed laminated wood) having improved impact resistance, flexibility and toughness are produced.
• the epoxy resin for example, compression molding, transfer molding and injection molding.
• composition having the above ratio of the epoxy resin (A) and the organic polymer (B) may be used as an adhesive with improved peel strength, a foam plastic with improved flexibility, a binding agent for a fiber board or a particle board, a coating, a binding agent for shell molding, a binder of a brake lining, a binder of a grindstone and a matrix resin of a composite material containing glass fiber or carbon fiber.
• the composition contains the organic polymer (A) in an amount larger than that of the epoxy resin (B), it is preferably molded by the same method as used for molding a solid rubber such as a natural rubber or a liquid elastomer such as polyurethane. Thereby, a molded elastomeric article and an expanded elastomeric article having improved strength are procuced.
• the composition having the above ratio of the epoxy resin (A) and the organic polymer (B) may be used as an adhesive with improved peel strength, a sealing agent anc a pressure sensitive adhesive.
• polypropyleneoxide (Average molecular weight, 3,000) (300 g) was charged followed by the addition of tolylenediisocyanate (26 g) and dibutyltin dilaurate (0.2 g). The mixture was stirred at 100°C for 5 hours in a stream of nitrogen gas. Then, Y-aminopropyltriethoxysilane (22.1 g) was added to the mixture and stirred at 100°C for 3 hours to obtain polyether having a triethoxysilyl group at a chain end and about two silicon-containing reactive groups in a molecule. Average molecular weight, about 6,600.
• the iodine number of the product was 2.0. Form this number, it was found that the product had, on the average, 1.2 silicon-containing reactive group and 0.6 polymerizable unsaturated group per molecule.
• n-butyl acrylate 95.4 g
• tris(2-hydroxyethyl)isocyanuric acid triacrylate 1.8 g
• Y-methacryloyloxypropyldimethoxy- methylsilane 1.5 g
• Y-mercaptopropyldimethoxymethylsilane 2.3 g
• AIBN 2,2'-azobisispbutyronitrile
• Butyl acrylate (80 g), vinyl acetate (20 g), Y-methacryloyloxypropylmethyldimethoxysilane (2.3 g), Y-mercaptopropylmethyldimethoxysilane (1.8 g) and azobis-2-(6-methyldiethoxysilyl-2-cyanohexane) (1.0 g) were homogeneously mixed. 25 g of the mixture was then charged in a four-necked 200 ml flask equipped with a stirrer and a condenser and heated at 80°C on an oil bath with introducing nitrogen gas. Within several minutes, the polymerization was initiated to generate heat. After the heat generation calmed, the rest of the mixture was dropwise added over 3 hours to proceed polymerization. After the heat generation ceased, the polymerization was terminated. The produced polymer had an average molecular weight of about 11,000 according to GPC analysis.
• Bisphenol A type epoxy resin (Epikote 828 (trade name) manufactured by Yuka Shell Epoxy Co., Ltd.) (50 parts), the polymer prepared in Preparation Example 2 (100 parts), 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) (1 part), 2,4,6-tris-(dimethylaminomethyl)phenol (2.5 parts), N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane (2.5 parts) and dibutyltin laurate (1 part) were thoroughly mixed and carefully poured in a polyethylene made frame so as to avoid the formation of bubbles. Then, the mixture was cured at 23°C for 7 days and post-cured at 50°C for 7 days to produce a sheet of the cured product having a thickness of 2 mm.
• T B was 7 kg/ cm 2 .
• T B was 5 kg/cm 2 .
• Example 3 In the same manner as in Example 1 but using a silicone compound in an amount as shown in Table 3 in place of N- ⁇ -(aminoethyl)- ⁇ -aminopropyltrimethoxysilane, a sheet of a cured product was produced. T B and E B of each sheet are shown in Table 3.
• Example 4 In the same manner as in Example 1 but using an epoxy resin and a curing agent in amounts as shown in Table 4, a sheet of a cured product was produced. T B and E B of each sheet are shown in Table 4.
• the polymer prepared in Preparation Example 1 25 parts, 2,2'-methylene-bis-(4-methyl-6-t-butylphenol) (0.5 part), Epikote 828 (100 parts), isophoronediamine (25 parts), water (0.05 part), dibutyltin dilaurate (1 part) and N-a-(aminoethyl)-Y-aminopropyltrimethoxysilane (4 parts) were thoroughly mixed and degassed. Then, the mixture was poured in polyethylene made frame and cured at 50°C for 1 day and then at 150°C for 2 hours. The Izod impact strength of the cured product was 6.1 Kg ⁇ cm/cm.
• the polymer prepared in Preparation Example 2 (100 parts), Epikote 828 (50 parts), a silane compound shown in Table 5, an epoxy resin curing agent shown in Table 5, a bisphenol type antioxidant (Noklack NS-6 manufactured by Ohuchi Shinko Kabushikikaisha) (1 part) and a silanol condensation catalyst shown in Table 5 were thoroughly mixed.
• the adhesive characteristics (tensile shear strength and T-shape peeling strength) of the mixture were evaluated according to the methods defined by JIS (Japanese Industrial Standard) K 6850 and K 6854.
• the mixture was coated in a thickness of about 0.05 mm.
• a pair of the same plates coated with the mixture were laminated with facing the coated surfaces to each other and pressed by hand.
• the laminated plates were kept at 23°C for one day and then at 50°C for three days and peeled off at a pulling rate of 50 mm/min. to measure the tensile shear strength.
• the mixture was coated in a thickness of about 0.5 mm.
• a pair of the same plates coated with the mixture were laminated with facing the coated surfaces to each other and pressed five times by moving a hand roller with 5 kg of load along the length in one direction.
• the laminated plates were kept at 23°C for one day and then at 50°C for three days and peeled off at a pulling rate of 200 mm/min. to measure the T-shape peeling strength.
• composition of Comparative Example 3 was the same as that of Example 13 except that the silane compound was not used.
• composition of Comparative Example 4 was the same as that of Example 19, 29 or 30 except that the organic polymer having silicon-containing reactive group and the silanol condensation catalyst were not used.
• the composition of Comparative Example 5 is a conventional adhesive composition of the epoxy resin.
• the polymer prepared in Preparation Example 2 was charged, evacuated under reduced pressure and flashed with a nitrogen gas. After heated to 90°C and stirred, a mixture of n-butyl acrylate (24.5 g), Y-mercaptopropylmethyldimethoxysilane (0.4 g) and AIBN (0.1 g) was dropwise added over 1 hour in an atmosphere of nitrogen. After 15 and 30 minutes from the completion of addition of the mixture, AIBN (each 0.0025 g dissolved in 4 time weight of acetone) was further added. Thereafter, the reaction mixture was stirred for 30 minutes to obtain a slightly yellowish viscous liquid polymer having Brookfield viscosity of 260 poise (23°C). According to the GC analysis, the amount of the unreacted monomers was 0.9 p.
• n-Butyl acrylate (95.84 g), Y-mercaptopropylmethyldimethoxysilane (2.02 g), Y-methacryloxypropylmethyldimethoxysilane (1.57 g), neopentylglycol diacrylate (0.30 g) and AIBN (0.25 g) were homogeneously mixed. 30 g of the mixture was then charged in a four-necked 200 ml flask equipped with a stirrer and a condenser and heated at 80°C on an oil bath with introducing nitrogen gas. Within several minutes, the polymerization was initiated to generate heat. After the heat generation calmed, the rest of the mixture was dropwise added over 3 hours to proceed polymerization.

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• 1985
  • 1985-12-23 US US06/812,378 patent/US4657986A/en not_active Expired - Lifetime
  • 1985-12-23 CA CA000498478A patent/CA1235245A/fr not_active Expired
  • 1985-12-24 DE DE8585116540T patent/DE3584007D1/de not_active Expired - Lifetime
  • 1985-12-24 EP EP85116540A patent/EP0186191B1/fr not_active Expired - Lifetime
  • 1985-12-25 JP JP60296313A patent/JPS61268720A/ja active Granted

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